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CRE 2 Week 10

The document discusses diffusion and reaction within catalyst particles, including concentration profiles, internal effectiveness factors, and their relationship to Thiele moduli for first order reactions in spherical, cylindrical axial, and cylindrical radial catalyst geometries.

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0% found this document useful (0 votes)
16 views23 pages

CRE 2 Week 10

The document discusses diffusion and reaction within catalyst particles, including concentration profiles, internal effectiveness factors, and their relationship to Thiele moduli for first order reactions in spherical, cylindrical axial, and cylindrical radial catalyst geometries.

Uploaded by

k.shilpya30
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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CE23332 Chemical Reaction

Engineering 2 (CRE 2/TRK 2)


Semester 2021-2

Week 10

Rehan Hussain, Ph.D.

1
Topics covered in 2nd half of semester
Week Title
Week 9 Diffusion and reaction
Week 10 Diffusion and reaction
Week 11 Diffusion and reaction
Week 12 Diffusion and reaction
Week 13 Bioreactor
Week 14 Residence time distributions (RTD)
Week 15 Review
Week 16 Final exam
Part 4. Diffusion & Reaction

Content Objectives
➢ Internal effectiveness factor ➢ Understand what the internal
effectiveness factor in a porous
catalyst represents and how it
varies under different conditions
➢ Be able to estimate the value of
effectiveness factor
1st order reaction in spherical catalyst
2 2 1 sinh 𝜙1 𝜆
𝑑 Ψ 2 𝑑Ψ 2 𝑑 𝑦 2
+ − 𝜙1 Ψ = 0 − 𝜙1 𝑦 = 0 Ψ=
𝑑𝜆2 𝜆 𝑑𝜆 𝑑𝜆2 𝜆 sinh 𝜙1

1st order reaction in cylindrical catalyst: diffusion in axial direction

2
𝑑 Ψ 2 cosh 𝜙1 𝜆 𝑧
− 𝜙1 Ψ = 0 Ψ= 𝜆=
𝑑𝜆2 cosh 𝜙1 𝐿

1st order reaction in cylindrical catalyst: diffusion in radial direction


2
𝑑 Ψ 1 𝑑Ψ
+ − 𝜙 2
Ψ = 0 𝐼𝑜 𝜙1 𝜆 𝑟
2 1 Ψ= 𝜆=
𝑑𝜆 𝜆 𝑑𝜆 𝐼𝑜 𝜙1 𝑅

Note: 𝐼𝑖 is a modified Bessel function of the first kind of order i.


Concentration profiles - 1storder reaction in a spherical
catalyst
1 sinh 𝜙1 𝜆 𝑟
Ψ= 𝐶𝐴 𝑅 sinh 𝜙1 𝑅
𝜆 sinh 𝜙1 =
𝐶𝐴𝑠 𝑟 sinh 𝜙1

Concentration varies with catalyst radius

Rate of reaction will also vary (except for


0-order reaction)
small 1: surface rxn control, significant amount
of reactant diffuses into pellet interior
w/out reacting
large 1: surface rxn is rapid, reactant is consumed
before reaching the center of the pellet (a
waste of precious metal catalyst inside of pellet)
Internal effectiveness factor (𝜂)
• In an ideal world, the concentration of the reactant inside the catalyst pellet would be
the same as the surface concentration. Thus, the rate of reaction inside the catalyst
pellet would be maximized.

• Instead, what we normally see is that the actual rate of reaction is lower than
expected due to mass transfer limitations.

• To quantify this, we define the internal effectiveness factor of the catalyst (ranging
from 0 to 1) as:

actual observed overall rate of rxn


𝜂=
rate of reaction if entire interior surface were exposed to CAs , Ts
Internal effectiveness factor (𝜂)
• In symbols, −𝑟𝐴 −𝑟′𝐴 −𝑟"𝐴
𝜂= = =
−𝑟𝐴𝑠 −𝑟′𝐴𝑠 −𝑟"𝐴𝑠

• The value of 𝜂 provides a measure of how far the reactant diffuses into the pellet
before reacting.
• The observed rate, −𝑟𝐴 , is also sometimes given the symbol −𝑟𝐴 (obs)
• The rates of reaction are often expressed in terms of absolute number of moles
converted per unit time:

−𝑟𝐴 −𝑟𝐴 × volume of catalyst particle 𝑀𝐴


𝜂= = =
−𝑟𝐴𝑠 −𝑟𝐴𝑠 × volume of catalyst particle 𝑀𝐴𝑠
Internal effectiveness factor (𝜂) - order reaction in a1st

spherical catalyst
In a spherical catalyst pellet,

𝑀𝐴𝑠 = −𝑟𝐴𝑠 × volume of catalyst particle


4 3
𝑀𝐴𝑠 = −𝑟𝐴𝑠 × 𝜋𝑅
3

For 1 st order reaction A → B −𝑟𝐴𝑠 = 𝑘𝐶𝐴𝑠

4 3
𝑀𝐴𝑠 = 𝑘𝐶𝐴𝑠 × 𝜋𝑅
3
Internal effectiveness factor (𝜂) - order reaction in a1st

spherical catalyst
• The actual rate of reaction is equal to the rate of diffusion of A into the pellet at the
outer surface, as all A going inside the catalyst reacts & no A diffuses back out:

2
𝑀𝐴 = −4𝜋𝑅 𝑊𝐴𝑟 ቚ
𝑟=𝑅

2
𝑑𝐶𝐴
→ 𝑀𝐴 = 4𝜋𝑅 𝐷𝑒 อ
𝑑𝑟
𝑟=𝑅

𝑑Ψ
→ 𝑀𝐴 = 4𝜋𝑅𝐷𝑒 𝐶𝐴𝑠 ቤ
𝑑𝜆 𝜆=1
Internal effectiveness factor (𝜂) for 1
order reaction in
st

a spherical catalyst
• For 1st order reaction

• Exercise 1: show that

• Hence, 𝑀𝐴 = 4𝜋𝑅𝐷𝑒 𝐶𝐴𝑠 ∅1 coth ∅1 − 1


Internal effectiveness factor (𝜂) - 1
order reaction in a
st

spherical catalyst
Recall that
• So far, we found that 𝑀𝐴 = 4𝜋𝑅𝐷𝑒 𝐶𝐴𝑠 ∅1 coth ∅1 − 1
4 3 𝑘1
𝑀𝐴𝑠 = 𝑘𝐶𝐴𝑠 × 𝜋𝑅 𝜙1 = 𝑅
3 𝐷𝑒

• Hence, 𝑀𝐴 4𝜋𝑅𝐷𝑒 𝐶𝐴𝑠 ∅1 coth ∅1 − 1


𝜂= =
𝑀𝐴𝑠 4 3
𝑘𝐶𝐴𝑠 × 𝜋𝑅
3
𝐷𝑒
𝜂 = 3 2 ∅1 coth ∅1 − 1
𝑘𝑅
1Τ∅12

3 Internal effectiveness factor for 1st


𝜂 = 2 ∅1 coth ∅1 − 1
∅1 order reaction in a spherical catalyst
Internal effectiveness & Thiele modulus in a spherical
catalyst
• Consider the variation of Thiele modulus for a sphere, s, for reactions of different orders:

As particle diameter ↓, s ↓, h→1, rxn is surface rxn limited


As particle diameter ↑, s ↑, h→0, rxn is diffusion limited

• Approximations for 1st order reaction:

3
• If ∅1 >2 → 𝜂 ≈ 2 ∅1 − 1
∅1
3
• If ∅1 >20 → 𝜂≈
∅1
Influence of catalyst particle geometry on concentration profile and
effectiveness factor for 1 order, isothermal, isobaric reaction
st

Cylindrical (axial Cylindrical (radial


Sphere
𝑟 direction) or slab direction)
𝜆= 𝑧 𝑟
𝑅 𝜆= 𝜆=
𝐿 𝑅

𝑘1 𝑘1 𝑘1
Thiele modulus 𝜙1 = 𝑅 𝜙1 = 𝐿 𝜙1 = 𝑅
𝐷𝑒 𝐷𝑒 𝐷𝑒

𝐶𝐴 1 sinh 𝜙1 𝜆 cosh 𝜙1 𝜆 𝐼𝑜 𝜙1 𝜆
Ψ= Ψ= Ψ= Ψ=
𝐶𝐴𝑠 𝜆 sinh 𝜙1 cosh 𝜙1 𝐼𝑜 𝜙1

Internal Effectiveness 𝜂 = 3 ∅ coth ∅ − 1 tanh ∅1 2 𝐼1 𝜙1


1 1 𝜂= 𝜂=
Factor 2
∅1 ∅1 𝜙1 𝐼𝑜 𝜙1

Note: 𝐼𝑖 is a modified Bessel function of the first kind of order i.


Internal effectiveness & Thiele modulus for 1 order
st

reaction in different pellet geometries

Note that as ∅1
becomes large, 𝜂 is
independent of
pellet geometry!
Internal effectiveness & Thiele Modulus

2
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
𝜙𝑛 =
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛

Once in the internal diffusion limited regime, changing factors that affect
the external mass transport rate (eg. fluid velocity) won’t affect the overall
rate of reaction
Actual reaction rate
• For1st order reaction that is limited by internal diffusion
3 3 𝐷𝑒
in spherical catalyst particles, the internal effectiveness 𝜂≈ =
factor (when ∅1 >20) can be approximated as: ∅1 𝑅 𝑘

• And the actual rate can be written as:

−𝑟𝐴 = 𝜂(−𝑟𝐴𝑠 )
So, to increase the rate (at a given T),
= 𝜂𝑘𝐶𝐴𝑠 we can:
• Decrease catalyst size
3 3 • Increase the external surface
−𝑟𝐴 = 𝐷𝑒 𝑘𝐶𝐴𝑠 or −𝑟𝐴 = 𝐷𝑒 𝑆𝑎 𝜌𝑐 𝑘"𝐶𝐴𝑠 concentration
𝑅 𝑅
• Increase internal surface area
Internal effectiveness factor (𝜂) for reactions other
than 1 order
st

• Thiele Modulus for spherical catalyst with n-th 2


𝑘𝑛 𝑅 𝐶𝐴𝑠 𝑛−1
2
order of reaction: 𝜙𝑛 =
𝐷𝑒

• For large values of Thiele Modulus

1/2 1/2
2 3 2 3 𝐷𝑒 (1−𝑛)/2
𝜂= 𝜂= 𝐶𝐴𝑠
𝑛+1 ∅𝑛 𝑛+1 𝑅 𝑘𝑛

Hence, the effectiveness factor decreases with increasing CAs for n > 1
Internal effectiveness factor (𝜂) for reactions with
volume change (𝜀 ≠ 0)
• Effectiveness factor ratios for1 st

order reaction on spherical catalyst

Example:
• For a gas phase reaction
A → 2B (𝜀=1)
if Thiele modulus = 10, then
𝜂′Τ𝜂=0.8
Internal effectiveness factor (𝜂)
for exothermic, non-isothermal 1 st

order reactions
• For exothermic, non-isothermal
reactions, it is possible to have 𝜂 > 1,
as the heat generated by reaction
inside the pellet can raise the
temperature above Ts, leading to
faster reaction rates.

• The value of 𝜂 depends on the


parameters γ (a.k.a the Arrhenius
number) and β (which represents the
maximum temperature difference in
the pellet relative to Ts).
Weisz-Prater criterion for internal diffusion
limitations
For 1st-order reaction in spherical catalyst,

3 2
𝜂 = 2 ∅1 coth ∅1 − 1 𝜂∅1 = 3 ∅1 coth ∅1 − 1
∅1
The term on the the LHS is Weisz-Prater parameter, denoted as 𝐶𝑊𝑃

2
𝐶𝑊𝑃 = 𝜂∅1

The Weisz–Prater criterion uses measured values of the observed reaction rate (−𝑟𝐴)
to check whether the reaction is limited by internal diffusion.
Weisz-Prater criterion for internal diffusion
limitations
Internal effectiveness factor and Thiele modulus have already been defined earlier,
as follows: 2 2
2
−𝑟𝐴𝑠 𝑅 −𝑟′𝐴𝑠 𝜌𝑐 𝑅
𝜙1 = =
𝐶𝐴𝑠 𝐷𝑒 𝐶𝐴𝑠 𝐷𝑒
Weisz-Prater parameter (1 st order reaction)

2
𝐶𝑊𝑃 = 𝜂∅1

If CWP<<1 → no diffusion limitation


Hence, If CWP>>1 → strongly limited by diffusion
Worked Example 1

(c) comment on the


significance of the results from
(a) and (b).
Exercise 2
A fluid ‘A’ reacts on a porous catalyst (‘B’) surface to form a product ‘C’. The bulk A
concentration is 0.1 M. The reaction is first order. The effective diffusivity of A in B
is De= 5×10 mm /s. The kinetic rate constant (accounting for surface area and
-3 2
10000

density of the catalyst) is 10 𝑒
12 𝑇 𝑠 −1
.The catalyst particle diameter is 5 mm.

a) Determine the Thiele modulus and the internal effectiveness factor of the reaction at
320 K. Do these conditions represent a reaction rate controlled or internal diffusion
controlled regime?
b) Calculate the observed rate of reaction at 320 K.
c) If particles of 2 mm diameter are used instead (keeping all other conditions fixed),
how much improvement would we see in the rate of reaction? What would be a
possible downside of making this change?

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